Ion-exchanged glass of high surface compression and shallow depth of layer with high resistance to radial crack formation from vickers indentation

ABSTRACT

Disclosed are alkali aluminosilicate glasses having unexpected resistance to indentation cracking. The glasses obtain this high resistance as a result of a high level of surface compression accompanied by a shallow depth of layer. The advantaged glasses show greater resistance to radial crack formation from Vickers indentation than glasses with the same compressive stress, but higher depths of layer.

This application is a continuation of U.S. application Ser. No. 14/547,456, filed on Nov. 19, 2014, which claims the benefit of priority to a continuation in part of U.S. application Ser. No. 13/533,298, filed on Jun. 26, 2012, which also claims the benefit of priority of U.S. Provisional Application Ser. No. 61/503,734, filed on Jul. 1, 2011; a continuation in part of U.S. application Ser. No. 13/678,013, filed on Nov. 15, 2012, which claims the benefit of priority of U.S. Provisional Application Ser. No. 61/560,434, filed on Nov. 16, 2011; and a continuation-in-part of U.S. application Ser. No. 14/456,354, filed on Aug. 11, 2014; and claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No. 61/907,121, filed on Nov. 21, 2013, the content of all is relied upon and all applications are incorporated herein by reference in their entireties.

FIELD

The disclosure relates to damage resistant glasses and more particularly, to damage resistant glasses that have optionally been strengthened by ion exchange. In some cases, the disclosure relates to damage resistant ion exchanged glasses having high surface compression while also having shallow depths of layer while still retaining a resistance to radial crack formation.

BACKGROUND

It is generally the case that ion-exchanged glass has higher resistance to radial crack formation from Vickers indentation when compared to non-strengthened glass of the same composition. The stress profile, in particular the magnitude of the compressive stress (the value of compressive stress at the surface, and is regarded as the maximum value, hereinafter “compressive stress” or “CS”) on the surface of the glass, plays a key role in this area. It is also traditionally been assumed that higher compressive stresses, and deeper depths of compression, will lead to enhanced performance. Equally important in controlling this behavior is the glass composition and structure/molar volume, both of which relate to the residual stresses and flaw population created by the indentation. While it is generally true that higher depth of layer (“DOL”)—the maximum depth of the compressive stress layer below the surface—results in enhanced performance especially with regard to retained strength, the current disclosure provides the unexpectedly unique result that for certain compositions and compressive stress levels, shallower DOLs bring the distinct and desirable attribute of higher resistance to indentation fracture.

SUMMARY

Disclosed are glasses for making a strengthened glass articles having a high indentation fracture threshold (“IFT”) at low DOLs and high CS. A first aspect comprises a glass for making a strengthened glass article, where the glass comprises an ion-exchangeable, boron-free, alkali aluminosilicate glass composition that is capable of achieving a compressive stress from about 600 to about 1200 MPa at a depth of layer from about 10 to about 40 μm and an indentation fracture threshold from about 10 to about 50 kg. In some cases, the compressive stress is from about 600 to about 1000 MPa, the depth of layer is from about 15 to about 30 μm, and the indentation fracture threshold is from about 12 to about 45 kg. In other cases, the compressive stress is from about 700 to about 1000 MPa, the depth of layer is from about 15 to about 25 μm, and the indentation fracture threshold is from about 14 to about 40 kg.

In some embodiments of the aspects herein, the glass composition comprises composition (1-1): 61 mol %≤SiO₂≤75 mol %; 7 mol %≤Al₂O₃≤15 mol %; 0 mol %≤B₂O₃≤1 mol %; 9 mol %≤Na₂O≤21 mol %; 0 mol %≤K₂O≤4 mol %; 0 mol %≤MgO≤7 mol %; and 0 mol %≤CaO≤3 mol %.   (1-1)

In some circumstances, the glass composition comprising composition (1-1), may further satisfy one or more of equations: 47 mol %≥B₂O₃+Na₂O+K₂O+MgO+CaO≥18 mol %; or 30 mol %≥B₂O₃+Na₂O+K₂O−Al₂O₃≥0.

Alternatively, the glass composition may comprise composition (2-1): about 50 mol % to about 75 mol % SiO₂; about 7 mol % to about 26 mol % Al₂O₃; 0 mol % to about 1 mol % B₂O₃; about 11 mol % to about 25 mol % Na₂O; 0 mol % to about 2.5 mol % K₂O; 0 mol % to about 8.5 mol % MgO; and 0 mol % to about 1.5 mol % CaO.   (2-1) Compositions comprising (2-1) may further satisfy one or more of equations: −340+27.1·Al₂O₃−28.7·B₂O₃+15.6·Na₂O−61.4·K₂O+8.1·(MgO+ZnO)≥0 mol %; Na₂O+Al₂O₃+MgO+ZnO>25 mol %; SiO₂+Al₂O₃+B₂O₃+Na₂O+K₂O+MgO+ZnO≥95 mol %; Na₂O+K₂O−Al₂O₃−MgO−ZnO≈0; or −5 mol %≤Na₂O+K₂O−Al₂O₃−MgO−ZnO≤4 mol %.

Another embodiment comprises a glass composition (3-1) comprising at least about 4 mol % P₂O₅ and less than about 1 mol % B₂O₃, and wherein: i. 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4; or ii. 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3;   (3-1) where M₂O₃=Al₂O₃+B₂O₃, R_(x)O is the sum of monovalent and divalent cation oxides present in the glass composition, and R₂O is the sum of monovalent cation oxides present in the glass composition. The glass composition may further comprise: about 40 mol % to about 70 mol % SiO₂; about 11 mol % to about 25 mol % Al₂O₃; about 4 mol % to about 15 mol % P₂O₅; 0 mol % to less than about 1 mol % B₂O₃; and about 13 mol % to about 25 mol % Na₂O.   (3-2) or, alternatively, may comprise: about 50 mol % to about 65 mol % SiO₂; about 14 mol % to about 20 mol % Al₂O₃; 0 mol % to less than about 1 mol % B₂O₃; about 4 mol % to about 10 mol % P₂O₅; and about 14 mol % to about 20 mol % Na₂O.   (3-3) The glass compositions of (3-1), (3-2), and (3-3) may optionally satisfy one or more of the equations: 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4; 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1; 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3; and 1.5<[(P₂O₅+R₂O)/M₂O₃]≤2.0. Additionally, The glass compositions of (3-1), (3-2), and (3-3) may optionally comprise less than 1 mol % K₂O or the monovalent and divalent cation oxides are selected from the group consisting of Li₂O, Na₂O, K₂O,Rb₂O, Cs₂O, MgO, CaO, SrO, BaO, and ZnO.

A second aspect comprises a glass article comprising any of the embodied glasses described herein.

A third aspect comprises a method of ion exchanging a glass composition having a layer under compressive stress, the layer extending from a surface of the glass article to a depth of layer, comprising providing any of the glass articles described herein and ion exchanging the glass article in a bath at a temperature of up to about 410° C. for from about 15 minutes to about 24 hours to form the layer, wherein the compressive stress of the layer is from about 600 MPa to about 1200 MPa and the depth of layer is from about 10 μm to about 40 μm. In some embodiments, the compressive stress is from about 600 to about 1000 MPa, the depth of layer is from about 15 to about 30 μm, and the indentation fracture threshold is from about 12 to about 45 kg. In some embodiments, the compressive stress is from about 700 to about 1000 MPa, the depth of layer is from about 15 to about 25 μm, and the indentation fracture threshold is from about 14 to about 40 kg.

A fourth aspect comprises a method of making a device comprising a glass article having a layer under compressive stress, the layer extending from a surface of the glass article to a depth of layer, comprising providing a glass article as described herein and ion exchanging the glass article in a bath at a temperature of up to about 410° C. for from about 15 minutes to about 24 hours to form the layer, wherein the compressive stress of the layer is from about 600 MPa to about 1200 MPa and the depth of layer is from about 10 μm to about 40 μm and the glass article is incorporated into a device. In some embodiments, the compressive stress is from about 700 to about 1000 MPa, the depth of layer is from about 15 to about 25 μm, and the indentation fracture threshold is from about 14 to about 40 kg.

These and other aspects, advantages, and salient features will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of a glass sheet strengthened by ion exchange;

FIG. 2 shows the variation in IFT with DOL for glass sample no. 141 at three different CS levels (˜450 MPa, ˜550 MPa, and ˜650 MPa);

FIG. 3 provides the IOX time dependence of indentation threshold, CS, and DOL for glass sample no. 26 ion-exchanged at 410° C. in KNO₃ salt bath. Note that DOL is scaled with IFT;

FIG. 4 shows the indentation threshold of glass sample no. 26 as a function of CS with the DOL constant at ˜41 μm;

FIG. 5 describes the indentation threshold of glass sample no. 26 as a function of DOL with CS constant at ˜820 MPa;

FIG. 6 is a graph of the CT dependence of indentation threshold of glass sample no. 26. Note that all the IFT data for the IOX conditions used in this work are plotted;

FIG. 7 provides the indentation threshold of glass sample no. 26 as a function of CS for high (>30 μm) and low (<30 μm) DOL;

FIG. 8 shows the test conditions for 120° dynamic indentation experiments on glass sample no. BG with various CS/DOL combinations;

FIG. 9 shows the indentation threshold for glass sample no. 141 with different DOL/CS at different IOX conditions.

DETAILED DESCRIPTION

Disclosed herein are alkali aluminosilicate glasses having unexpected resistance to indentation cracking (which we will call indentation fracture threshold (IFT) from here onward). The glasses obtain this high IFT, at least in part, as a result of a high level of surface compression accompanied by a shallow depth of layer. The advantage of a high CS and shallow DOL is that it leads to greater resistance to radial crack formation from Vickers indentation than the same CS with a higher DOL. This is beneficial when high resistance to the initiation of radial cracking is the primary objective, such as in the case of an electronic device, where the resistance of the cover glass to indentation cracking would help prevent crack propagation and thus, increase the likelihood that a user could continue to use the device even after the screen has been subjected to substantial impact damage.

Further, disclosed are materials, compounds, compositions, and components that can be used for, can be used in conjunction with, can be used in preparation for, or are embodiments of the disclosed method and compositions. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be explicitly disclosed, each is specifically contemplated and described herein.

Thus, if a class of substituents A, B, and C are disclosed as well as a class of substituents D, E, and F, and an example of a combination embodiment, A-D is disclosed, then each is individually and collectively contemplated. Thus, in this example, each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and/or C; D, E, and/or F; and the example combination A-D. Likewise, any subset or combination of these is also specifically contemplated and disclosed. Thus, for example, the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and/or C; D, E, and/or F; and the example combination A-D. This concept applies to all aspects of this disclosure including, but not limited to any components of the compositions and steps in methods of making and using the disclosed compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination is specifically contemplated and should be considered disclosed.

In addition, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those elements recited, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of a group of elements or combinations thereof, it is understood that the group may consist of any number of those elements recited, either individually or in combination with each other.

Moreover, where a range of numerical values is recited herein, comprising upper and lower values, unless otherwise stated in specific circumstances, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the disclosure be limited to the specific values recited when defining a range. Further, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed. Finally, when the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to.

As used herein, the term “about” means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such.

The term “or”, as used herein, is inclusive; more specifically, the phrase “A or B” means “A, B, or both A and B”. Exclusive “or” is designated herein by terms such as “either A or B” and “one of A or B”, for example.

The indefinite articles “a” and “an” are employed to describe elements and components of embodiments. The use of these articles means that one or at least one of these elements or components is present. Although these articles are conventionally employed to signify that the modified noun is a singular noun, as used herein the articles “a” and “an” also include the plural, unless otherwise stated in specific instances. Similarly, the definite article “the”, as used herein, also signifies that the modified noun may be singular or plural, again unless otherwise stated in specific instances.

For the purposes of describing the embodiments, it is noted that reference herein to a variable being a “function” of a parameter or another variable is not intended to denote that the variable is exclusively a function of the listed parameter or variable. Rather, reference herein to a variable that is a “function” of a listed parameter is intended to be open ended such that the variable may be a function of a single parameter or a plurality of parameters. It is also understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not to be construed as limiting terms.

It is noted that terms like “preferably,” “commonly,” and “typically,” when utilized herein, are not utilized to limit the scope or to imply that certain features are critical, essential, or even important to the structure or function of the embodiments described. Rather, these terms are merely intended to identify particular aspects of an embodiment or to emphasize alternative or additional features that may or may not be utilized in a particular embodiment.

For the purposes of describing and defining embodiments it is noted that the terms “substantially” and “approximately” are utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The terms “substantially” and “approximately” are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

It is noted that one or more of the claims may utilize the term “wherein” as a transitional phrase. For the purposes of defining embodiments, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

As a result of the raw materials and/or equipment used to produce the glass composition, certain impurities or components that are not intentionally added, can be present in the final glass composition. Such materials are present in the glass composition in minor amounts and are referred to herein as “tramp materials.”

As used herein, a glass composition having 0 wt % or mol % of a compound is defined as meaning that the compound, molecule, or element was not purposefully added to the composition, but the composition may still comprise the compound, typically in tramp or trace amounts. Similarly, “sodium-free,” “alkali-free,” “potassium-free” or the like are defined to mean that the compound, molecule, or element was not purposefully added to the composition, but the composition may still comprise sodium, alkali, or potassium, but in approximately tramp or trace amounts. Unless otherwise specified, the concentrations of all constituents recited herein are expressed in terms of mole percent (mol %).

Indentation fracture threshold (IFT) is measured by using a Vickers indenter. The Vickers indenter is a square based diamond pyramid having four faces, with the included angle between opposite faces of 136°. The technique (see, e.g., D. J. Morris, S. B. Myers, and R. F. Cook, “Indentation crack initiation in ion-exchanged aluminosilicate glass,” 39 J. MAT. So. 2399-2410 (2004), herein incorporated by reference in its entirety) involves making multiple indentations with a Vickers indenter at a constant load. IFT measurements described herein are performed by applying and then removing an indentation load to the glass surface at a rate of 0.2 mm/min wherein the indentation load is held for 10 seconds and the maximum load. All indentation measurements are performed at room temperature in 50% relative humidity. The IFT is defined at the indentation load at which 50% of indents at a load exhibit any number of radial/median cracks emanating from the corners of the indent impression. The maximum load is increased until the threshold is met for a given glass composition.

Referring to the drawings in general and to FIG. 1 in particular, it will be understood that the illustrations are for the purpose of describing particular embodiments and are not intended to limit the disclosure or appended claims thereto. The drawings are not necessarily to scale, and certain features and certain views of the drawings may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.

Glass Compositions

The ion-exchanged glasses disclosed herein have unexpected resistance to IFT at high CS and shallow DOL. Glass compositions which are able to achieve this unique property are generally alkali aluminosilicate glasses, particularly alkali aluminosilicate glasses that do not contain boron. More specifically, the glass compositions embodied herein include those non-boron containing compositions specified in U.S. application Ser. Nos. 12/856,840, 13/533,298, and 13/677,805, all of which are hereby incorporated by reference in their entireties. For example, one embodied glass composition able to achieve high IFT at high CS and shallow DOL comprises SiO₂ and Na₂O, wherein SiO₂+B₂O₃≥66 mol %, and Na₂O≥9 mol %. The glass, in some embodiments, further comprises at least one of K₂O, MgO, and CaO. In a particular embodiment, the glass comprises: 61 mol %≤SiO₂≤75 mol %; 7 mol %≤Al₂O₃≤15 mol %; 0 mol %≤B₂O₃≤1 mol %; 9 mol %≤Na₂O≤21 mol %; 0 mol %≤K₂O≤4 mol %; 0 mol %≤MgO≤7 mol %; and 0 mol %≤CaO≤3 mol %. Embodiments may further meet the criteria that: 47 mol %≥B₂O₃+Na₂O+K₂O+MgO+CaO≥18 mol %; or 30 mol %≥B₂O₃+Na₂O+K₂O−Al₂O₃≥0. The glass, in some embodiments, may additionally comprise at least one fining agent such as, but not limited to, a halogen or a multivalent fining agent such as As₂O₃, Sb₂O₃, SnO₂, or Fe₂O₃. In a particular embodiment, the total concentration of As₂O₃ and Sb₂O₃, if either or both are present, is less than 500 ppm by weight.

Alternatively, other embodied glass compositions that are able to achieve resistance to IFT at high CS and shallow DOL include compositions comprising at least about 50 mol % SiO₂ and at least about 11 mol % Na₂O. In some embodiments, the glass article comprises: about 50 mol % to about 75 mol % SiO₂; about 7 mol % to about 26 mol % Al₂O₃; about 0 mol % B₂O₃; about 11 mol % to about 25 mol % Na₂O; 0 mol % to about 2.5 mol % K₂O; 0 mol % to about 8.5 mol % MgO; and 0 mol % to about 1.5 mol % CaO. Embodiments may further meet the criteria that: −340+27.1·Al₂O₃−28.7·B₂O₃+15.6·Na₂O−61.4·K₂O+8.1·(MgO+ZnO)≥0 mol %; Na₂O+Al₂O₃+MgO+ZnO>25 mol %; or SiO₂+Al₂O₃+B₂O₃+Na₂O+K₂O+MgO+ZnO≥95 mol %. In some embodiments, the aluminosilicate glass article described herein comprises SiO₂, Na₂O, Al₂O₃, and at least one of K₂O, MgO and ZnO, and wherein Na₂O+Al₂O₃+MgO+ZnO>25 mol %. Additionally, in some embodiments, be desirable that most of the alkali metal oxides in the glass articles described herein can be accounted for as charge-balancing cations for aluminum, magnesium and zinc; i.e., Na₂O+K₂O−Al₂O₃−MgO−ZnO≈0. In the same way that the relative proportions of Na, K, Al, Mg, and Zn oxides may be varied to achieve various ion exchange effects, B₂O₃ and CaO may be used in combination with variations in the oxides of the above elements to improve manufacturing attributes. While not necessarily a condition needed for the compositions herein, some embodiments satisfy the criterion: −5 mol %≤Na₂O+K₂O−Al₂O₃−MgO−ZnO≤4 mol %.

Other embodied glass compositions comprise an alkali aluminosilicate glass comprising at least about 4 mol % P₂O₅ and less than about 1 mol % B₂O₃ and wherein: i. 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4; or ii. 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3; where M₂O₃=Al₂O₃+B₂O₃, R_(x)O is the sum of monovalent and divalent cation oxides present in the alkali aluminosilicate glass, and R₂O is the sum of monovalent cation oxides present in the alkali aluminosilicate glass. Particular compositions that meet the above criteria and are embodied herein include alkali aluminosilicate glasses comprising: about 40 mol % to about 70 mol % SiO₂; about 11 mol % to about 25 mol % Al₂O₃; about 4 mol % to about 15 mol % P₂O₅; 0 mol % to less than about 1 mol % B₂O₃; and about 13 mol % to about 25 mol % Na₂O. or, alternatively: about 50 mol % to about 65 mol % SiO₂; about 14 mol % to about 20 mol % Al₂O₃; 0 mol % to less than about 1 mol % B₂O₃; about 4 mol % to about 10 mol % P₂O₅; and about 14 mol % to about 20 mol % Na₂O. In some embodiments, the glasses above satisfy the equation 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4 or 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1. In other cases, the embodied glass satisfies 1.3<[(P₂O₅+R₂O)/M₂O₃]≥2.3, or 1.5<[(P₂O₅+R₂O)/M₂O₃]≤2.0. Embodiments may further meet one or more of the criteria that the alkali aluminosilicate glass further comprises less than 1 mol % K₂O or the monovalent and divalent cation oxides are selected from the group consisting of Li₂O, Na₂O, K₂O,Rb₂O, Cs₂O, MgO, CaO, SrO, BaO, and ZnO.

Specific example glass compositions embodied herein are shown in TABLE 1, a compilation of some of the compositions shown in Tables 1 and 2 from U.S. application Ser. No. 12/856,840 and Table 1 of U.S. application Ser. No. 13/533,298, and TABLE 2, which shows a cross-section of compositions embodied herein that are shown in Tables 1 and 2 from U.S. application Ser. No. 13/677,805, all of which are hereby incorporated by reference in their entireties. All values are in mol % unless otherwise stated.

TABLE 1 Sam- ple SiO₂ Al₂O₃ B₂O₃ Na₂O K₂O MgO CaO ZnO SnO₂ 1 67.34 12.33 0 20.33 0 0 0 0 2 67.85 9.21 0.54 14.16 2.34 5.22 0.46 0.19 3 68.07 9.72 0.57 13.21 2.31 5.39 0.54 0.18 4 68.68 9.54 0.56 12.92 2.27 5.29 0.53 0.18 5 69.25 9.03 0.39 13.41 2.21 5.04 0.47 0.18 6 70.25 8.86 0 13.43 1.67 5.18 0.41 0.17 7 70.19 8.6 0 14.28 1.19 5.1 0.44 0.18 8 70.72 8.67 0 13 2.16 5.19 0.05 0.17 9 69.96 8.60 0.55 14.03 1.21 4.97 0.45 0.20 10 69.85 8.71 0.05 14.27 1.26 5.18 0.47 0.19 11 69.86 8.65 0.03 14.17 1.2 5.05 0.49 0.18 12 70.11 8.68 0.03 14.22 1.2 5.06 0.49 0.18 13 69.25 9.03 0.39 13.41 2.21 5.04 0.47 0.18 14 69.41 8.55 0 14.05 1.19 6.17 0.44 0.19 15 70.92 8.52 0 13.7 1.17 5.11 0.36 0.19 16 64.87 9.18 0.8 14.42 4.99 5.5 0.07 0.15 17 72.16 8.13 0 13.27 1.03 4.81 0.42 0.16 18 73.51 7.6 0 11.58 2.3 4.2 0.6 0.2 19 73.14 7.19 0 12.54 2.16 4.72 0.05 0.18 20 73.52 7.6 0 13.87 0 4.2 0.61 0.2 21 65 11.25 0.6 14.25 2.35 5.75 0.6 0.2 22 64 12.25 0.6 14.25 2.35 5.75 0.6 0.2 23 64 11.25 0.6 14.25 2.35 5.75 1.6 0.2 24 62 12.25 0.6 14.25 2.35 5.75 2.6 0.2 25 66 12.25 0.6 14.25 0.35 3.75 2.6 0.2 26 69.19 8.52 0 13.94 1.17 6.44 0.54 0.19 27 66 11.3 0.6 14.2 1.4 5.7 0.6 0.2 28 72.55 8.2 0 11.8 2.3 4.35 0.6 0.2 29 71.6 8.85 0 12 2.3 4.45 0.6 0.2 30 70.7 9.45 0 12.2 2.3 4.55 0.6 0.2 31 69.75 10.05 0 12.4 2.3 4.7 0.6 0.2 32 69.87 8.77 0.56 12.67 2.27 5.14 0.53 0.18 33 71.04 8 0.56 12.42 2.27 4.99 0.53 0.18 34 72.22 7.22 0.56 12.17 2.27 4.84 0.53 0.18 35 70.43 8.77 0 12.67 2.27 5.14 0.53 0.18 36 71.61 7.99 0 12.42 2.27 4.99 0.53 0.18 37 72.78 7.22 0 12.17 2.27 4.84 0.53 0.18 38 71.61 7.99 0 12.95 2.27 4.99 0 0.18 39 72.22 7.22 0 12.17 3.36 4.84 0 0.18 40 72.22 7.22 0 14.26 2.27 3.84 0 0.18 41 72.22 7.22 0 13.26 3.27 3.84 0 0.18 42 73.5 7.6 0 12.75 1.15 4.2 0.6 0.2 43 73.5 7.6 0 13.9 0 4.2 0.6 0.2 44 72.55 8.2 0 12.95 1.15 4.35 0.6 0.2 45 72.55 8.2 0 14.1 0 4.35 0.6 0.2 46 73.94 7.65 0 13.98 0 4.23 0 0.2 47 72.98 8.25 0 14.19 0 4.38 0 0.2 48 73.5 7.6 0 11.6 2.3 4.2 0.6 0.2 49 62.93 12.99 5 16.98 2 0 0 0.1 50 67.73 9.7 0.62 13.3 2.37 5.54 0.48 0.18 51 68.67 8.54 0.56 13.96 2.27 5.29 0.53 0.18 52 71.15 7.78 0.51 12.93 2.09 4.87 0.49 0.18 53 71.16 8.03 0 13.18 2.09 4.87 0.49 0.18 54 68.67 9.68 0 13.37 2.27 5.29 0.53 0.18 55 68.67 9.54 0 13.51 2.27 5.29 0.53 0.18 56 71.27 8.24 0 12.9 2.08 4.85 0.48 0.17 57 67.2 12.31 0 20.29 0 0 0 0.2 58 67.01 12.35 0.36 20.08 0 0 0 0.2 59 66.82 12.38 0.72 19.88 0 0 0 0.2 60 68.32 11.82 0.69 18.97 0 0 0 0.2 61 67.77 10.84 0.36 20.83 0 0 0 0.2 62 67.57 10.88 0.72 20.63 0 0 0 0.2 63 67.2 11.31 0 19.29 0 2 0 0.2 64 67.02 11.34 0.36 19.08 0 2 0 0.2 65 66.82 11.38 0.72 18.88 0 2 0 0.2 66 68.7 10.74 0 18.36 0 2 0 0.2 67 68.52 10.78 0.34 18.16 0 2 0 0.2 68 68.31 10.82 0.69 17.98 0 2 0 0.2 69 66.14 10.19 0.58 14.16 2.37 5.75 0.59 0.21 70 66 12.3 0.6 14.2 0.35 4.75 1.6 0.2 71 68.67 10.04 0.56 12.46 2.27 5.29 0.53 0.18 72 69.06 9.59 0 13.03 2.28 5.32 0.53 0.18 73 68.7 11.74 0 19.36 0 0 0 0.2 74 68.52 11.78 0.34 19.16 0 0 0 0.2 75 67.96 13.05 0 18.79 0 0 0 0.2 76 67.78 13.08 0.36 18.58 0 0 0 0.2 77 67.58 13.12 0.72 18.38 0 0 0 0.2 78 69.57 8.43 0 13.95 1.16 6.18 0.5 0.18 79 69.9 8.3 0 13.81 1.15 6.14 0.49 0.18 80 69.4 8.36 0 14.29 1.06 6.18 0.5 0.18 81 69.95 8.23 0 14.01 1.04 6.07 0.5 0.18 82 69.21 9.02 0 12.98 0.02 7.52 1.05 0 0.2 83 70.43 9.07 0 13.09 0.02 7.13 0.06 0 0.19 84 70.57 9.07 0 12.06 0.96 7.07 0.06 0 0.19 85 69.29 9.39 0 13.12 0.6 7.33 0.07 0 0.18 86 69.5 9.35 0 13.14 0.47 7.28 0.07 0 0.18 87 69.7 9.4 0 13.05 0.47 7.12 0.07 0 0.18 88 69.51 9.28 0 13.2 0.47 7.28 0.07 0 0.18 89 68.84 9.83 0 13.07 0.93 7.06 0.07 0 0.18 90 69.32 9.25 0 13.15 0.65 7.36 0.07 0 0.18 91 69.86 10.05 0 12.61 0.97 6.23 0.05 0 0.19 92 68.62 9.85 0 13.74 0.49 7.04 0.07 0 0.18 93 69.88 9.28 0 13.01 0.6 6.97 0.06 0 0.18 94 70.17 9.09 0 12.02 0.98 6.53 1 0 0.2 95 68.93 10.23 0 14.13 0.01 6.43 0.07 0 0.2 96 71.24 9.25 0 12.07 0.98 6.2 0.05 0 0.19 97 66.82 9.48 0 14.47 0.78 8.18 0.08 0 0.18 98 68.15 9.75 0 14 0.59 7.25 0.07 0 0.18 99 69.63 9.08 0 12.97 0.95 7.09 0.07 0 0.2 100 71.3 9.15 0 13.05 0.01 6.23 0.05 0 0.19 101 68.17 9.16 0 13.98 0.69 7.74 0.07 0 0.18 102 69.52 9.03 0 13.04 0.95 7.18 0.06 0 0.19 103 70 9.35 0 13.27 0.49 6.63 0.06 0 0.18 104 71.52 9.06 0 12.06 0.97 6.13 0.05 0 0.2 105 71.56 9.06 0 13.03 0.02 6.07 0.06 0 0.19 106 69.59 10.04 0 13.05 0.96 6.1 0.05 0 0.19 107 69.13 9.86 0 13.55 0.76 6.44 0.07 0 0.18 108 69.77 9.47 0 12.69 1.11 6.26 0.49 0 0.18 109 69.79 8.48 0 12.67 1.12 7.24 0.49 0 0.18 110 69.73 8.5 0 13.69 0.17 7.22 0.48 0 0.18 111 69.75 9.48 0 13.68 0.15 6.25 0.48 0 0.18 112 69.64 9.14 0 12.8 0.97 6.28 0.96 0 0.2 113 68.12 10.29 0 15.06 0.02 6.24 0.05 0 0.19 114 68.72 10.18 0 14.77 0.02 6.06 0.05 0 0.18 115 68.81 8.85 0 13.64 1.09 7.33 0.06 0 0.17 116 69.76 9.57 0 12.35 1.91 6.15 0.06 0 0.19 117 68.61 10.17 0 14.86 0.02 6.08 0.05 0 0.18 118 68.45 8.46 0 13.68 1.12 7.6 0.49 0 0.18 119 68.4 10.14 0 14.98 0.01 6.19 0.07 0 0.19 120 68.33 10.13 0 15.05 0.02 6.21 0.05 0 0.18 121 70.58 10.06 0 13.04 0.96 5.1 0.05 0 0.19 122 69.12 10.14 0 14.56 0.13 5.78 0.06 0 0.18 123 68.82 10.19 0 14.85 0.01 5.85 0.06 0 0.2 124 70.64 9.02 0 12.05 1.88 6.15 0.05 0 0.19 125 68.26 10.38 0 15.14 0.02 5.94 0.05 0 0.19 126 68.55 10.4 0 15.04 0.01 5.73 0.06 0 0.2 127 70.58 9.01 0 13.06 0.96 6.14 0.05 0 0.19 128 69.18 10.27 0 14.7 0.01 5.57 0.06 0 0.2 129 70.65 8.06 0 13.02 0.97 7.03 0.06 0 0.19 130 68.28 10.61 0 14.34 0.81 5.68 0.08 0 0.19 131 70.74 8.49 0 13.63 0.17 6.28 0.49 0 0.18 132 68.44 10.44 0 15.12 0.05 5.69 0.05 0 0.19 133 70.09 9.08 0 14.31 0.01 6.23 0.07 0 0.2 134 68.03 10.08 0 15.33 0.04 6.26 0.06 0 0.18 135 68.36 10.14 0 15.19 0.02 6.04 0.05 0 0.18 136 69.72 9.49 0 13.12 1.45 5.95 0.08 0 0.18 137 70.79 9.06 0 13.99 0.02 5.89 0.05 0 0.19 138 70.8 8.48 0 12.68 1.12 6.23 0.48 0 0.18 139 69.09 10.24 0 14.83 0.05 5.55 0.05 0 0.18 140 68.23 10.56 0 15.31 0.01 5.64 0.05 0 0.19 141 69.96 10.28 0 15.21 0.01 5.37 0 0 0.17 142 68.08 9.66 0 15 0.34 6.54 0.17 0 0.18 143 68.46 10.53 0 14.71 0.49 5.54 0.07 0 0.19 144 68.8 9.48 0 13.67 1.11 6.23 0.48 0 0.18 145 69.09 9.79 0 14.86 0.01 5.98 0.05 0 0.2 146 68.06 9.95 0 15.28 0.13 6.28 0.09 0 0.18 147 67.29 11.27 0 15.82 0.01 5.35 0.05 0 0.2 148 68.54 10.14 0 15.18 0.01 5.89 0.05 0 0.18 149 66.37 12.04 0 16.29 0.01 5.03 0.05 0 0.21 150 68.74 10.22 0 15.12 0.01 5.66 0.05 0 0.18 151 68.62 10.2 0 14.97 0.24 5.71 0.05 0 0.19 152 71.42 8.97 0 12.46 1.36 5.54 0.06 0 0.18 153 64.42 13.5 0 17.28 0.01 4.54 0.05 0 0.2 154 68.34 10.43 0 15.13 0.2 5.62 0.05 0 0.19 155 62.63 14.99 0 18.22 0.01 3.91 0.04 0 0.2 156 68.94 10.1 0 15.07 0.01 5.62 0.05 0 0.18 157 70.67 8.16 0 12.78 0.97 6.22 0.99 0 0.2 158 70.67 9.17 0 12.83 0.95 5.19 0.98 0 0.2 159 68.21 10.54 0 15.31 0.16 5.51 0.05 0 0.19 160 69.83 8.49 0 13.19 1.12 6.19 0.98 0 0.18 161 69.78 8.49 0 13.67 1.12 6.66 0.07 0 0.18 162 68.41 10.45 0 15.15 0.31 5.42 0.05 0 0.19 163 69.2 10.19 0 15.08 0.01 5.27 0.05 0 0.18 164 68.21 10.65 0 15.61 0.01 5.26 0.06 0 0.2 165 69.57 9.02 0 13.99 0.96 6.2 0.06 0 0.19 166 69.38 10.16 0 15.03 0.01 5.15 0.06 0 0.2 167 69.62 10.1 0 14.93 0.01 5.1 0.05 0 0.18 168 68.55 10.39 0 15.07 0.42 5.3 0.05 0 0.19 169 69.6 9.06 0 13.07 1.92 6.09 0.05 0 0.19 170 69.71 8.03 0 13.01 1.92 7.07 0.06 0 0.2 171 69.32 10.08 0 15.12 0.01 5.23 0.05 0 0.18 172 69.26 8.54 0 13.82 1.12 6.55 0.52 0 0.18 173 69.31 10.29 0 15.14 0.01 5.01 0.05 0 0.18 174 68.78 10.19 0 14.92 0.49 5.35 0.05 0 0.19 175 71.68 9.04 0 13.02 0.95 5.06 0.05 0 0.19 176 71.61 8.07 0 13.04 0.97 6.05 0.05 0 0.19 177 69.72 8.5 0 13.67 1.13 6.28 0.48 0 0.18 178 69.83 8.47 0 12.69 2.07 6.25 0.48 0 0.18 179 69.26 8.78 0 15.01 0.22 6.43 0.06 0 0.2 180 69.69 8.5 0 14.65 0.17 6.3 0.48 0 0.18 181 69.27 8.55 0 14.97 0.01 6.47 0.52 0 0.19 182 69.94 10.26 0 15.06 0.01 4.48 0.04 0 0.17 183 69.92 10.09 0 15.12 0.01 4.62 0.04 0 0.18 184 69.74 8.5 0 13.7 0.63 6.24 0.98 0 0.18 185 69.8 8.48 0 14.66 1.1 5.28 0.48 0 0.18 186 69.85 8.49 0 13.68 1.6 6.1 0.06 0 0.18 187 68.76 8.51 0 14.65 1.12 6.29 0.48 0 0.18 188 69.72 8.46 0 14.16 1.11 6.27 0.07 0 0.18 189 69.27 8.49 0 13.69 1.12 6.24 0.98 0 0.18 190 70.72 7.49 0 13.68 1.12 6.29 0.49 0 0.18 191 69.62 8.66 0 14.4 0.7 6.33 0.06 0 0.2 192 70.24 8.48 0 13.66 1.11 6.23 0.06 0 0.18 193 70.64 9.02 0 13.03 1.9 5.15 0.05 0 0.19 194 70.8 8.49 0 13.65 1.09 5.28 0.48 0 0.18 195 69.84 9.46 0 13.66 1.11 5.23 0.48 0 0.18 196 69.61 8.56 0 13.9 1.16 6.08 0.47 0 0.19 197 67.48 9.21 0 14.5 1.46 6.29 0.88 0 0.18 198 69.85 7.47 0 13.64 1.12 7.23 0.48 0 0.17 199 68.69 8.48 0 13.66 2.07 6.41 0.48 0 0.18 200 70.8 8.03 0 13.96 0.96 6 0.05 0 0.2 201 69.88 8.48 0 13.66 2.07 5.21 0.49 0 0.18 202 70.55 9.05 0 14.04 0.97 5.14 0.05 0 0.19 203 68.79 8.83 0 13.94 1.36 6.01 0.88 0 0.18 204 50.7 25.5 0 23.7 0.01 0.02 0.06 0 0.01 205 69.01 10.86 0 14.63 0.01 5.26 0.05 0 0.16 206 68.89 10.7 0 14.73 0.01 5.09 0.05 0.37 0.16 207 68.71 10.66 0 14.83 0.01 4.91 0.04 0.65 0.16 208 68.73 10.66 0 14.84 0.01 4.63 0.04 0.91 0.16 209 68.75 10.63 0 14.9 0.01 4.37 0.04 1.13 0.16 210 68.86 10.65 0 14.74 0.01 4.15 0.04 1.37 0.16 211 68.98 10.66 0 14.71 0.01 3.64 0.04 1.79 0.16 212 68.95 10.65 0 14.74 0.01 3.49 0.05 1.93 0.17 213 68.62 10.76 0 14.91 0.01 3.53 0.04 1.94 0.16 214 68.21 10.92 0 15.09 0.01 3.57 0.04 1.98 0.17 215 68.12 11.18 0 15.01 0.01 3.52 0.04 1.94 0.16 216 68.34 10.84 0 14.87 0.01 3.47 0.04 2.25 0.16 217 68.71 10.71 0 14.79 0.01 3.2 0.04 2.37 0.16 218 68.29 11 0 15.09 0.01 3 0.04 2.39 0.16 219 67.94 11.05 0 15.25 0.01 3.05 0.03 2.48 0.16 220 67.93 11.01 0 15.28 0.01 3.26 0.04 2.29 0.16

TABLE 2 Example Number A B C D E F G SiO₂ in mol % 61.0 59.0 57.0 62.0 60.0 58.0 58.0 Al₂O₃ in mol % 15.5 16.5 17.5 15.5 16.5 17.5 17.4 P₂O₅ in mol % 7.0 7.0 7.0 6.0 6.0 6.0 6.1 Na₂O in mol % 16.5 17.5 18.5 16.5 17.5 18.5 18.5 MgO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.1 ZnO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 SnO₂ in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (M₂O₃)/R_(x)O in mol % 0.94 0.94 0.95 0.94 0.94 0.95 0.95 (P₂O₅ + R₂O)/(M₂O₃) 1.52 1.48 1.46 1.45 1.42 1.40 1.41 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.52 1.48 1.46 1.45 1.42 1.40 1.40 in mol % Density (g/cm³) 2.388 2.401 2.412 2.393 2.406 2.416 2.416 Molar Volume 30.41 30.43 30.47 30.01 30.03 30.08 30.08 (cm³/mol) Strain Pt. (° C.) 615 620 625 633 638 640 640 Anneal Pt. (° C.) 675 678 682 693 697 699 699 Softening Pt. (° C.) 963 958 951 973 978 969 969 Temperature at 200 P 1732 1708 1683 1752 1720 1698 1698 Viscosity (° C.) Temperature at 35 kP 1284 1274 1260 1304 1289 1275 1275 Viscosity (° C.) Temperature at 160 1195 1186 1176 1215 1202 1191 1191 kP Viscosity (° C.) Liquidus 775 740 730 770 790 770 890 Temperature (° C.) Liquidus Viscosity 2.91E+10 8.74E+10 4.40E+11 1.67E+11 2.46E+10 2.04E+11 7.09E+08 (P) Example Number H I J K L M N SiO₂ in mol % 60.0 60.0 60.0 60.0 60.0 60.0 62.0 Al₂O₃ in mol % 16.0 16.0 16.0 16.0 16.0 16.0 15.0 P₂O₅ in mol % 5.0 5.0 6.0 6.0 7.0 7.0 5.0 Na₂O in mol % 16.0 16.0 16.0 16.0 16.0 16.0 15.0 MgO in mol % 3.0 0.0 2.0 0.0 1.0 0.0 3.0 ZnO in mol % 0.0 3.0 0.0 2.0 0.0 1.0 0.0 SnO₂ in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 CaO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (M₂O₃)/R_(x)O in mol % 0.84 0.84 0.89 0.89 0.94 0.94 0.83 (P₂O₅ + R₂O)/(M₂O₃) 1.31 1.31 1.38 1.38 1.44 1.44 1.33 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.50 1.50 1.50 1.50 1.50 1.50 1.53 in mol % Density (g/cm³) 2.417 2.453 2.406 2.428 2.393 2.404 2.423 Molar Volume 29.21 29.28 29.76 29.83 30.35 30.38 28.95 (cm³/mol) Strain Pt. (° C.) 643 621 623 619 611 621 680 Anneal Pt. (° C.) 696 681 684 681 675 683 730 Softening Pt. (° C.) 964 954.3 963.5 963.4 965 967.4 989.1 Temperature at 200 P 1668 1677 1695 1698 1714 1713 1676 Viscosity (° C.) Temperature at 35 kP 1247 1252 1268 1265 1280 1277 1252 Viscosity (° C.) Temperature at 160 1162 1166 1181 1178 1193 1190 1167 kP Viscosity (° C.) Liquidus 960 1100 Temperature (° C.) Liquidus Viscosity 1.85E+07 6.28E+05 (P) Example Number O P Q R S T U SiO₂ in mol % 60.3 62.3 61.3 60.8 60.5 62.2 62.1 Al₂O₃ in mol % 15.9 14.7 15.7 16.0 15.9 14.6 14.6 P₂O₅ in mol % 5.5 4.9 5.0 5.0 5.2 5.0 5.0 Na₂O in mol % 16.2 15.0 16.0 16.1 16.3 15.1 15.2 MgO in mol % 1.9 2.0 1.9 2.0 2.0 3.1 0.1 ZnO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 3.0 SnO₂ in mol % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CaO in mol % 0.0 1.0 0.0 0.0 0.0 0.1 0.0 (M₂O₃)/R_(x)O in mol % 0.88 0.82 0.87 0.88 0.87 0.80 0.80 (P₂O₅ + R₂O)/(M₂O₃) 1.36 1.36 1.34 1.32 1.35 1.37 1.38 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.48 1.56 1.46 1.45 1.47 1.59 1.59 in mol % Density (g/cm³) 2.415 2.415 2.414 2.417 2.416 2.413 2.449 Molar Volume 29.49 29.07 29.30 29.31 29.40 29.02 29.10 (cm³/mol) Strain Pt. (° C.) 632 644 638 639 636 652 614 Anneal Pt. (° C.) 688 695 694 696 694 702 671 Softening Pt. (° C.) 965.7 980.7 975.7 972.1 970.6 977.2 950 Temperature at 200 P 1690 1699 1703 1698 1691 1704 1702 Viscosity (° C.) Temperature at 35 kP 1267 1267 1278 1275 1269 1263 1253 Viscosity (° C.) Temperature at 160 1181 1179 1191 1189 1183 1178 1167 kP Viscosity (° C.) Example Number V W X Y Z AA AB SiO₂ in mol % 60.0 60.4 60.2 62.8 61.3 61.1 60.9 Al₂O₃ in mol % 15.6 15.6 15.5 14.4 15.1 15.2 15.3 P₂O₅ in mol % 5.5 5.0 4.9 4.1 4.7 4.8 4.9 Na₂O in mol % 16.3 16.4 16.4 15.6 15.7 15.8 15.8 MgO in mol % 2.5 2.5 2.9 3.0 3.0 3.0 3.0 ZnO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 SnO₂ in mol % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CaO in mol % 0.0 0.0 0.1 0.0 0.0 0.0 0.0 (M₂O₃)/R_(x)O in mol % 0.83 0.83 0.80 0.77 0.81 0.81 0.81 (P₂O₅ + R₂O)/(M₂O₃) 1.39 1.37 1.38 1.37 1.35 1.35 1.35 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.55 1.53 1.57 1.58 1.55 1.55 1.55 in mol % Density (g/cm³) 2.419 2.421 2.427 2.422 2.422 2.422 2.422 Molar Volume 29.35 29.17 29.00 28.58 28.92 28.98 29.03 (cm³/mol) Strain Pt. (° C.) 619 624 632 653 635 634 632 Anneal Pt. (° C.) 672 677 680 704 685 684 682 Softening Pt. (° C.) 954.2 956.8 952.6 977.4 963.1 961.8 957.4 Temperature at 200 P 1675 1680 1659 1709 1693 1690 1689 Viscosity (° C.) Temperature at 35 kP 1246 1255 1229 1263 1257 1256 1254 Viscosity (° C.) Temperature at 160 1161 1169 1145 1176 1170 1170 1168 kP Viscosity (° C.) Example Number AC AD AE AF AG AH AI SiO₂ in mol % 61.8 56.9 60.1 60.2 60.1 61.1 61.0 Al₂O₃ in mol % 13.5 13.4 15.0 15.4 15.2 14.6 14.9 P₂O₅ in mol % 5.0 10.0 6.0 5.4 5.7 5.4 5.5 Na₂O in mol % 19.5 19.6 15.7 15.9 15.9 15.2 15.5 MgO in mol % 0.0 0.0 3.0 3.0 3.0 3.5 3.1 ZnO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 SnO₂ in mol % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CaO in mol % 0.0 0.0 0.1 0.1 0.1 0.1 0.1 (M₂O₃)/R_(x)O in mol % 0.69 0.68 0.80 0.81 0.80 0.78 0.80 (P₂O₅ + R₂O)/(M₂O₃) 1.82 2.21 1.44 1.38 1.42 1.41 1.41 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.82 2.21 1.64 1.58 1.62 1.65 1.62 in mol % Density (g/cm³) 2.426 2.408 2.413 2.419 2.416 2.415 2.415 Molar Volume 28.96 30.85 29.45 29.23 29.34 29.10 29.21 (cm³/mol) Strain Pt. (° C.) 574 522 626 637 630 649 639 Anneal Pt. (° C.) 625 568 679 688 681 701 689 Softening Pt. (° C.) 872.9 825.1 947.3 955.1 949.9 969.4 961 Temperature at 200 P 1651 1587 1686 1679 1684 1678 1698 Viscosity (° C.) Temperature at 35 kP 1162 1126 1248 1253 1248 1248 1256 Viscosity (° C.) Temperature at 160 1075 1040 1162 1169 1163 1163 1172 kP Viscosity (° C.) Liquidus 990 915 1000 Temperature (° C.) Example Number AJ AK AL AM AN AO AP SiO₂ in mol % 56.4 55.5 56.2 56.3 57.4 57.3 56.4 Al₂O₃ in mol % 17.4 17.4 16.5 14.5 16.6 14.5 16.5 P₂O₅ in mol % 8.0 8.9 8.0 7.9 7.0 6.9 7.9 Na₂O in mol % 18.1 18.0 18.1 18.0 17.8 18.1 19.0 MgO in mol % 0.1 0.1 1.0 3.1 1.0 3.0 0.0 ZnO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 SnO₂ in mol % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CaO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 (M₂O₃)/R_(x)O in mol % 0.96 0.97 0.86 0.69 0.88 0.69 0.87 (P₂O₅ + R₂O)/(M₂O₃) 1.50 1.54 1.59 1.79 1.50 1.72 1.62 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.50 1.55 1.65 2.00 1.56 1.93 1.62 in mol % Density (g/cm³) 2.41 2.41 2.42 2.43 2.42 2.43 2.42 Molar Volume 30.82 31.19 30.54 29.86 30.16 29.49 30.58 (cm³/mol) Strain Pt. (° C.) 603 591 586 571 601 588 586 Anneal Pt. (° C.) 661 648 642 619 658 634 642 Softening Pt. (° C.) 932.5 916.5 909.5 877.4 928.3 900.7 906.5 Temperature at 200 P 1653 1660 1641 1603 1660 1616 1644 Viscosity (° C.) Temperature at 35 kP 1227 1224 1214 1171 1233 1183 1212 Viscosity (° C.) Temperature at 160 1142 1138 1128 1086 1148 1098 1126 kP Viscosity (° C.) Liquidus 800 Temperature (° C.) Example Number AQ AR AT AU AV AW AX SiO₂ in mol % 59.2 59.3 59.3 59.3 59.2 59.3 58.4 Al₂O₃ in mol % 15.0 14.8 15.1 14.8 14.6 15.1 16.0 P₂O₅ in mol % 6.8 6.8 6.8 6.8 6.8 6.7 6.8 Na₂O in mol % 15.2 14.9 15.1 14.9 14.8 15.2 15.9 MgO in mol % 3.1 3.0 3.5 3.6 3.6 3.6 2.7 ZnO in mol % 0.5 1.0 0.0 0.5 1.0 0.0 0.0 SnO₂ in mol % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CaO in mol % 0.1 0.1 0.1 0.1 0.1 0.0 0.0 (M₂O₃)/R_(x)O in mol % 0.80 0.78 0.81 0.78 0.75 0.80 0.86 (P₂O₅ + R₂O)/(M₂O₃) 1.46 1.47 1.45 1.46 1.48 1.45 1.41 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.71 1.74 1.69 1.74 1.80 1.69 1.58 in mol % Density (g/cm³) 2.43 2.41 2.41 2.42 2.43 2.411 2.414 Molar Volume 29.61 29.79 29.71 29.59 29.48 29.64 29.87 (cm³/mol) Strain Pt. (° C.) 615 613 617 620 620 616 612 Anneal Pt. (° C.) 669 663 668 671 669 669 666 Softening Pt. (° C.) 936.3 934.5 939.7 938.2 942.5 940.7 940.2 Temperature at 200 P 1667 1666 1663 1670 1657 1666 1661 Viscosity (° C.) Temperature at 35 kP 1241 1234 1233 1235 1216 1240 1243 Viscosity (° C.) Temperature at 160 1156 1148 1147 1151 1133 1153 1158 kP Viscosity (° C.) Liquidus Temperature (° C.) Example Number AY AZ BA BB BC BD BE SiO₂ in mol % 59.2 58.4 57.9 57.1 56.5 56.8 57.4 Al₂O₃ in mol % 16.1 16.5 16.8 17.2 17.6 16.8 16.6 P₂O₅ in mol % 5.8 6.2 6.5 6.9 7.3 7.1 7.1 Na₂O in mol % 16.6 17.0 17.3 17.7 18.0 17.1 16.7 MgO in mol % 2.2 1.7 1.3 0.9 0.5 2.1 2.1 ZnO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 SnO₂ in mol % 0.1 0.1 0.1 0.1 0.1 0.1 0.1 CaO in mol % 0.1 0.0 0.0 0.0 0.0 0.0 0.1 (M₂O₃)/R_(x)O in mol % 0.86 0.88 0.90 0.93 0.95 0.88 0.88 (P₂O₅ + R₂O)/(M₂O₃) 1.39 1.40 1.42 1.43 1.44 1.44 1.43 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.53 1.51 1.49 1.48 1.47 1.56 1.56 in mol % Density (g/cm³) 2.418 2.415 2.416 2.416 2.414 2.419 2.415 Molar Volume 29.58 29.86 30.07 30.30 30.54 30.14 30.14 (cm³/mol) Strain Pt. (° C.) 624 618 616 616 615 609 610 Anneal Pt. (° C.) 681 677 675 674 674 666 666 Softening Pt. (° C.) 954.9 950.5 948.1 947.9 949.3 930.8 940.6 Temperature at 200 P 1680 1673 1676 1670 1667 1654 1660 Viscosity (° C.) Temperature at 35 kP 1257 1253 1254 1250 1249 1235 1240 Viscosity (° C.) Temperature at 160 1171 1168 1169 1166 1164 1151 1156 kP Viscosity (° C.) Liquidus 955 Temperature (° C.) Example Number BF BG BH BI BJ BK BL SiO₂ in mol % 58.2 57.8 57.9 56.8 56.9 56.9 56.8 Al₂O₃ in mol % 16.1 16.5 16.3 16.5 16.8 17.0 17.5 P₂O₅ in mol % 6.3 6.5 6.4 6.5 6.4 6.4 6.4 Na₂O in mol % 15.9 16.5 16.3 16.5 16.8 17.1 17.1 MgO in mol % 3.5 2.6 3.0 3.6 3.1 2.5 2.0 ZnO in mol % 0.0 0.0 0.0 0.0 0.0 0.0 0.0 SnO₂ in mol % 0.1 0.1 0.1 0.0 0.0 0.0 0.0 CaO in mol % 0.1 0.1 0.1 0.0 0.0 0.0 0.0 (M₂O₃)/R_(x)O in mol % 0.83 0.86 0.84 0.82 0.84 0.86 0.91 (P₂O₅ + R₂O)/(M₂O₃) 1.38 1.39 1.39 1.40 1.38 1.38 1.34 in mol % (P₂O₅ + R_(x)O)/(M₂O₃) 1.60 1.55 1.58 1.62 1.56 1.53 1.46 in mol % Density (g/cm³) 2.421 2.419 2.420 2.426 2.426 2.424 2.420 Molar Volume 29.58 29.82 29.72 29.64 29.70 29.81 30.00 (cm³/mol) Strain Pt. (° C.) 615 616 616 615 615 623 624 Anneal Pt. (° C.) 666 671 670 666 669 679 681 Softening Pt. (° C.) 937.8 945.7 941.6 930.6 933.9 949.7 952.4 Temperature at 200 P 1655 1658 1658 1641 1646 1646 1657 Viscosity (° C.) Temperature at 35 kP 1235 1236 1236 1224 1233 1236 1246 Viscosity (° C.) Temperature at 160 1152 1154 1154 1141 1151 1152 1162 kP Viscosity (° C.)

The compressive layer (or layers) of the glass article may be formed by ion exchanging the glass article as shown, for example in U.S. application Ser. Nos. 12/856,840 and 13/533,298, both of which are hereby incorporated by reference in their entireties. In a particular embodiment, ion exchange is carried out by immersing the glass article in a molten salt bath substantially comprising potassium nitrate (KNO₃). The ion exchange bath may also comprise up to about 0.6 mol % and, in some embodiments, up to about 0.2 mol % sodium nitrate (NaNO₃). As used herein, the term “substantially comprising” means that other components may be present in the molten salt bath. Such components may include, but are not limited to, compounds that act to reduce attack of the bath vessel or the glass article by the molten salt. Such additional components may include, but are not limited to, selected components of the glass, such as silicic acid, alumina in gel form, silica in gel form, or the like.

An embodiment comprises a method of strengthening an alkali aluminosilicate glass, the method comprising: providing an alkali aluminosilicate glass as described above, and immersing the alkali aluminosilicate glass in an ion exchange bath for a time period from about 15 minutes to up to about 24 hours to form a compressive layer extending from a surface of the alkali aluminosilicate glass to a depth of layer of from about 10 μm to about 40 μm, about 10 μm to about 35 μm, about 10 μm to about 30 μm, about 10 μm to about 25 μm, about 10 μm to about 20 μm, about 15 μm to about 35 μm, about 15 μm to about 30 μm, about 15 μm to about 25 μm, or about 15 μm to about 20 μm.

The temperature of the molten salt bath in which the aluminosilicate glass article described herein is immersed is less than or equal to about 420° C., in other embodiments, less than or equal to about 415° C., and, is still other embodiments, less than about 410° C. This temperature may be determined, for example, by embedding or otherwise containing a suitable thermocouple within an electrically insulating sheath and submerging the thermocouple in the molten salt bath at a depth roughly corresponding to the depth at which the glass article will be immersed during the ion exchange process. The glass article is immersed in the KNO₃ ion exchange bath for a time period of up to, in some embodiments, about eight hours. In other embodiments, the glass article is immersed in the KNO₃ ion exchange bath for a time period from about 15 minutes to about 16 hours.

The process of annealing a glass causes the rate of ion exchange of the glass article to increase while causing the compressive stress of the compressive layer to increase. Due to the increase in ion exchange time, however, it is often impractical to take advantage of such an annealing process. In addition, ion exchange at lower temperatures reduces the rate of stress relaxation of the ion exchanged glass, thereby increasing the compressive stress in the glass article. However, ion exchange at lower temperature decreases the rate of ion exchange, thus making it impractical to carry out ion exchange at lower temperature due to the long times required to ion exchange the glass to a desired depth of layer.

In some embodiments, the aluminosilicate glass described herein is annealed prior to ion exchange. Unless otherwise specified, “anneal” means holding the glass a temperature that is between the strain point and glass transition temperature Tg of the glass for a period of up to about two hours and then cooled at a rate of up to about 1° C./minute to room temperature (i.e., about 25° C.). Alternatively, the aluminosilicate glass may be rapidly cooled (i.e., at a rate of at least about 4° C./second) from a high temperature to a temperature below the strain point of the glass or directly to room temperature. Such rapid cooling may occur when the glass is formed by a down draw process such as slot or fusion draw processes. The aluminosilicate glass article is typically heated to a first temperature that is greater than the anneal point of the glass to increase the volume of the glass, and then quenched to a second temperature that is less than the strain point of the glass. In one embodiment in which the glass article is molten, the melt is heated to a temperature that is greater than the anneal point and quenched by down-drawing the glass using, for example, slot-draw or fusion-draw processes, to form a sheet. In other embodiments, a solid glass article is heated to a temperature above the anneal point of the glass and then quenched to a temperature below the strain point of the glass.

FIG. 1 schematically provides a cross-sectional view of a portion (i.e., ends of the glass sheet are not shown) of a glass sheet strengthened by ion exchange. In the non-limiting example shown in FIG. 1, strengthened glass sheet 100 has a thickness t, central portion 130, and a first surface 110 and second surface 112 that are substantially parallel to each other. Compressive layers 120, 122 extend from first surface 110 and second surface 112, respectively, to depths of layer d₁, d₂ below each surface. Compressive layers 120, 122 are under a compressive stress, while central portion 130 is under a tensile stress, or in tension. The tensile stress in central portion 130 balances the compressive stresses in compressive layers 120, 122, thus maintaining equilibrium within strengthened glass sheet 100. In some embodiments, the glasses and glass articles described herein may be ion exchanged to achieve a compressive stress of at least about 600 MPa and/or a depth of compressive layer of from about 15 μm to about 50 μm, and have an IFT of from about 10 to about 20 kg or more. In some embodiments, the glasses and glass articles described herein may be ion exchanged to achieve a compressive stress of at least about 500 MPa and/or a depth of compressive layer of at least about 40 μm. In some embodiments, the glass is ion exchanged to achieve a compressive stress of at least about 500, 550, 600, 625, 650, 675, 700, 750, 800, or 1000 MPa.

In some embodiments, the glass is ion exchanged to achieve a depth of layer from about 10 μm to about 40 μm, about 10 μm to about 35 μm, about 10 μm to about 30 μm, about 10 μm to about 25 μm, about 10 μm to about 20 μm, about 15 μm to about 35 μm, about 15 μm to about 30 μm, about 15 μm to about 25 μm, about 15 μm to about 20 μm, about 15 μm to about 50 μm, about 20 μm to about 45 μm, or about 25 μm to about 40 μm. The depth of layer in some embodiments may be about 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm or may fall within a range defined by these values or any numerical value within these values.

In addition to the high CS at low DOL, the ion exchanged alkali aluminosilicate glasses embodied herein have an IFT when measured using a Vickers indenter of at least about 10 kg. In some embodiments, the ion exchanged alkali aluminosilicate glasses have an IFT of at least about 10, 12, 14, 16, or 18 kg. Other embodied compositions have an IFT of from about 10 to about 30 kg, about 12 to about 30 kg, about 14 to about 30 kg, or about 16 to about 30 kg.

Alternatively, the crack resistance may be measured using the Vickers indentation crack initiation load of the Vickers indenter. In some embodiments, the ion exchanged alkali aluminosilicate glasses have a Vickers indentation crack initiation load of at least about 10, 15, or 20 kgf. In some embodiments, the ion exchanged alkali aluminosilicate glasses have a Vickers indentation crack initiation load of at least about 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 45 or 50 kgf. Embodiments may have a Vickers indentation crack initiation load from about 10 to about 50 kgf, about 14 to about 50 kgf, about 18 to about 50 kgf, or about 20 to about 50 kgf.

The embodiments described herein may a CS of from about 600 to about 1200 MPa, a DOL from about 15 to about 40 μm, and an IFT from about 10 to about 40 kg. Alternatively, embodiments may have a CS of from about 600 to about 1000 MPa, a DOL from about 15 to about 30 μm, and an IFT from about 12 to about 40 kg. Still other embodiments may have a CS of from about 700 to about 1000 MPa, a DOL from about 15 to about 25 μm, and an IFT from about 14 to about 40 kg. Further embodiments may have a CS of from about 800 to about 1000 MPa, a DOL from about 15 to about 25 μm, and a Vickers indentation crack initiation load from about 12 to about 40 kgf.

As noted previously, the ion-exchanged glass compositions disclosed herein have unexpected resistance to IFT at high CS and shallow DOL. The fact that these glasses obtain a higher fracture threshold having a high CS and a shallow depth of layer relative to progressively deeper DOL is counter-intuitive to traditional understandings of IFT. While not wanting to be held to any specific theory, a mechanistic explanation of the effect of CS/DOL interplay on the IFT characteristics is attempted herein.

The deformation response of deeper DOL vs. shallower DOL at the same depth below the surface where the compressive stress of the former is higher, must be considered to account for the higher indentation fracture threshold of the latter as stated above. Kato et al., (Y. Kato et al. “Effect of densification on crack initiation under Vickers indentation test,” 356 J. Non-Crystalline Solids 1768-1773 (2010) and Y. Kato et al., “Load dependence of densification in glass during Vickers indentation test,” 119 J. Ceram. Soc. Japan 110-115 (2011), both of which are hereby incorporated by reference in their entireties) carried out Vickers indentation fracture testing on various commercial glasses. The permanent deformation associated with an indentation is the result of two types of responses of the glass i.e., densification and shear (or “plastic”) flow. It is widely accepted that crack initiation is affected by the amount of shear flow taking place around the indentation. If shear deformation is too it may cause shear-flow related cracks. However, Kato et al. did not find any correlation between ease of deformation (as indicted by indentation hardness measurements) and crack resistance. Instead, they found a correlation between densification and crack resistance. They postulated that densification reduces the severity of stress concentration via the reduction in the interstitial space of the 3-dimensional network by a decrease in atomic bond angle and distance. In testing this theory, they found that the higher the recoverable densification, the higher the crack initiation threshold.

However, in contrast to Kato et al., in the embodied compositions it was found that the % elastic recovery is similar in both the high CS/high DOL and embodied high CS/shallow DOL (TABLE 3).

TABLE 3 % Elastic Depth CS (MPa) DOL (μm) Recovery (%) Std. Dev. (%) 452 27 81.3 1.0 451 40 82.3 0.5 555 26 81 0.4 556 33 81.7 0.6 556 41 82 0.4 680 21 81.9 1.4 648 27 81.9 2.3 679 33 83.5 0.7 650 40 84.2 0.8

Thus is postulated that the lower cracking threshold of the higher DOL/high CS glasses compared with the embodied shallow DOL/high CS must be a result of the phenomenon of densification followed by cracking in the elastic regime. In contrast, the shallow DOL/high CS glass allowed more densification without the resulting cracking the elastic regime. Also, the volume of glass “available” for densification in the case of the “shallow DOL” is greater than in the “deep DOL” due to the composition and stress profile. This larger “free” volume is proposed to be critically responsible for the higher IFT in the “shallow DOL,” but is only present when the surface CS is near and/or above about 600 MPa.

EXAMPLES Example 1

TABLE 4 lists a series of example alkali aluminosilicate glass coupons made with glass sample no. 26 that have been ion-exchanged under various conditions to produce specimens with varying DOL and CS. Electron microprobe work was carried out to determine the composition profile of the glass after ion exchange. Compressive stress and DOL were obtained by using FSM data in combination with modeling. As it may be evidenced in the data, two variables were varied i.e., the CS and DOL. CS was varied between approximately 400 MPa and 700 MPa, and DOL was varied from approximately 20 to 40 μm. FIG. 2 presents a summary chart where the IFT values of glasses with a variety of combination of CS and DOL has been presented.

TABLE 4 CS (MPa) DOL (μm) IFT (Kg) mean ± 1σ 452 27 5.5 ± 1.0 451 40 4.8 ± 1.2 555 26 5.5 ± 0.0 556 33 6.8 ± 0.6 556 41 6.5 ± 0.0 680 21 10.5 ± 2.6  648 27 8.5 ± 0.0 679 33 7.5 ± 0.0 650 40 5.5 ± 1.0

Example 2

The effect shown in Example 1 is observed in other alkali aluminosilicate glasses as well, such as glass sample no. 141, when varying the CS/DOL. TABLE 5 shows these results. However, note the testing was only conducted up to 10 kg, so the actual IFT was never determined.

TABLE 5 CS (MPa) DOL (μm) IFT (Kg) 734 38 6.5 690 23 >10 824 26 >10

Example 3

High IFT values were also measured at even higher CS (higher than that reported in TABLE 2) and shallower DOL to confirm that observation, see TABLE 6. The data in TABLE 4 confirm that the effect of high CS/shallow DOL in improving the IFT performance of the glass compositions described herein is real.

TABLE 6 CS (MPa) DOL (μm) IFT (Kg) mean ± 1σ 883 14 17.5 ± 0.0 841 14 19.0 ± 3.0

Example 4

Glass sample no. 26 with thickness of 1 mm is chosen as the model material in order to differentiate the respective role of CS and DOL in determining IFT of ion-exchanged glass. Three types of IOX experiments are designed: (1) varied IOX time periods at fixed IOX temperature, (2) varied DOL but fixed CS to examine the effect of DOL, and (3) varied CS but fixed DOL to examine the effect of CS. Fixed CS or DOL is achieved by tuning IOX temperature and time. All the IOX experiments are performed in technical grade KNO₃ bath. CS and DOL are measured by FSM and a Vickers indenter is used in the IFT test.

Generally, two types of failure are observed at the IFT load depending on the extent of IOX. Radial cracks appear at the IFT load for a glass with brief IOX that produces low CS and shallow DOL. However, a glass with a greater extent of IOX breaks at the IFT load along with forming radial cracks near the indentation impression region. The IFT of glass sample no. 26 shows a non-monotonic relationship with IOX time, CS, and DOL, as shown in FIG. 3. The IFT is only ˜5 kgf at a short IOX time of ˜5 min, then reaches a maximum of ˜17.5 kgf, and finally abruptly drops to ˜6 kgf This last value is relatively unaffected by further increases in IOX time. As shown in FIG. 3, except for the low CS at very short IOX times (˜5.5 min.), both CS and DOL are a monotonic function of IOX time.

The dependences of IFT on CS and DOL is further examined by setting DOL and CS, as shown in FIGS. 4 and 5, respectively. Surprisingly, the IFT of glass sample no. 26 is roughly unaffected even as the CS varies in a wide range from 600˜800 MPa. The IFT of glass sample no. 26 is large when the CS is large and the DOL is shallow (<30 μm), but decreases dramatically to ˜6 kgf and remains nearly unchanged as DOL increases further (FIG. 7). The effect of CT on IFT was also examined, in which all the IFT data for the IOX experiments used in this work are plotted (FIG. 6). Low, and nearly constant, IFT is found at CT>28 MPa. The IFT of glass sample no. 26 reaches a plateau when the CT is beyond a certain value, as seen in FIG. 6. This also explains the plateau region at longer IOX time in FIG. 3, at larger DOL in FIG. 5, and the independence of IFT on CS in FIG. 4.

Example 5

The quasi-static Vickers indentation threshold was examined for glass sample no. BG at the three following CS and DOL conditions for as-drawn glass: 1.) CS=959 MPa, DOL=47 microns, 2.) CS=974 MPa, DOL=25 microns, and 3.) CS=690 MPa, DOL=66 microns. The results are given in TABLE 7.

TABLE 7 Compressive Depth of Central Vickers Indentation Stress (MPa) Layer (microns) Tension (MPa) Threshold (kgf) 959 47 50 15-20 974 25 26 40-45 690 66 52 10-15 As can be seen in TABLE 7, the Vickers indentation threshold is clearly improved for ion-exchange with DOL<30 μm and with the lowest CT value.

A dynamic indentation experiment was also performed with a sharper 120° 4-sided pyramidal indenter tip to study high rate, sharp contact failure. The intent of this test was to determine if the advantage of high CS (>750 MPa), low DOL (<30 microns) still holds under other contact conditions besides for quasi-static Vickers indentation. Three test conditions were used as shown in FIG. 8. The results of the experiment are given in TABLE 8.

TABLE 8 As-drawn glass with As-drawn glass with As-drawn glass with Annealed glass with Velocity Indentation CS = 959 MPa, DOL = CS = 974 MPa, DOL = CS = 690 MPa, DOL = CS = 1064 MPa, DOL = (mm/s) Load (kgf) 47 microns 25 microns 66 microns 25 microns Test Condition 1 143 ± 5 14.6 ± 0.5  0% Failed  0% Failed 100% Failed 100% Failed Test Condition 2 192 ± 8 19.6 ± 0.8 50% Failed 40% Failed Test Condition 3 240 ± 5 24.5 ± 0.5 100% Failed  100% Failed 

The results indicate that under these test conditions there is no improvement in the high CS (974 MPa) shallow DOL (25 micron) parts when compared to high CS (959 MPa) deep DOL (46 microns) parts. Both are failing at the same or nearly the same frequency under each test condition. It is clear, however, that both as-drawn, high CS samples offer a substantial advantage over the as-drawn lower CS (690 MPa), very deep DOL (66 microns) samples who fail 100% of the time under test condition 1. The expectation is that the resistance to failure under this contact condition can be improved for samples with even higher CS at 25 micron DOL, although this may eventually be limited by the increasing CT. In an attempt to verify this theory, a samples of glass no. BG were annealed prior to ion-exchange and a CS of 1064 MPa and DOL of 25 μm was achieved, However, the resistance to failure decreased as shown by a 100% failure rate under test condition number 1. The likely cause for the reduction in resistance to failure is the removal of free volume and therefore reduction of inherent damage resistance during the annealing process.

The CS/DOL indentation experiments on glass sample BG show that the high CS/low DOL condition offers an improvement to quasi-static indentation results and give equivalent performance to the same glass (w/same thermal history) with the same CS and deeper DOL in dynamic 120° indentation.

Example 6

IFT versus DOL at various CS was tested in glass sample no. 141 and the results plotted in FIG. 9. As the figure shows, glass sample no. 141 showed high IFT at low DOL (˜15 μm)and high (˜841 MPa) values as compared to IFT values at various CS with DOLs around 40-60 μm.

While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure or appended claims. 

What is claimed is:
 1. A glass article comprising: 40 mol % to 70 mol % SiO₂; 11 mol % to 25 mol % Al₂O₃; at least 4 mol % to 15 mol % P₂O₅; less than 1 mol % B₂O₃; less than 1 mol % K₂O; and from 13 mol % to 25 mol % Na₂O.
 2. The glass article of claim 1, wherein: i. 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4; or ii. 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3, where M₂O₃=Al₂O₃+B₂O₃, R_(x)O is the sum of monovalent and divalent cation oxides present in the glass composition, and R₂O is the sum of monovalent cation oxides present in the glass composition.
 3. The glass article of claim 1, wherein the glass article is ion-exchange strengthened with a compressive stress from 600 to 1200 MPa at a depth of layer from 10 to 40 μm and an indentation fracture threshold from 10 to 50 kg.
 4. The glass article of claim 1, wherein the glass article satisfies one or more of: 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4; 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1; 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3; and 1.5<[(P₂O₅+R₂O)/M₂O₃]≤2.0. where M₂O₃=Al₂O₃+B₂O₃ R_(x)O is the sum of monovalent and divalent cation oxides present in the glass composition, and R₂O is the sum of monovalent cation oxides present in the glass composition.
 5. The glass article of claim 4, wherein the monovalent and divalent cation oxides are selected from the group consisting of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, MgO, CaO, SrO, BaO, and ZnO.
 6. A method of ion exchanging a glass article having a layer under compressive stress, the layer extending from a surface of the glass article to a depth of layer, comprising: providing the glass article of claim 1; and ion exchanging the glass article in a bath at a temperature of up to 410° C. for from 15 minutes to 24 hours to form the layer, wherein the compressive stress of the layer is from 600 MPa to 1200 MPa and the depth of layer is from 10 μm to 40 μm.
 7. A method of making a device comprising a glass article having a layer under compressive stress, the layer extending from a surface of the glass article to a depth of layer, comprising: providing the glass article of claim 1; ion exchanging the glass article in a bath at a temperature of up to 410° C. for from 15 minutes to 24 hours to form the layer, wherein the compressive stress of the layer is from 600 MPa to 1200 MPa and the depth of layer is from 10 μm to 40 μm; and incorporating the glass article into a device.
 8. A glass article comprising: 50 mol % to about 65 mol % SiO₂; 14 mol % to about 20 mol % Al₂O₃; 0 mol % to less than about 1 mol % B₂O₃; 0 mol % to less than about 1 mol % K₂O; 4 mol % to about 10 mol % P₂O₅; and from 14 mol % to 20 mol % Na₂O.
 9. The glass article of claim 8, wherein: i. 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4; or ii. 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3, where M₂O₃=Al₂O₃+B₂O₃, R_(x) O is the sum of monovalent and divalent cation oxides present in the glass composition, and R₂O is the sum of monovalent cation oxides present in the glass composition.
 10. The glass article of claim 8, wherein the glass article is ion-exchange strengthened with a compressive stress from 600 to 1200 MPa at a depth of layer from 10 to 40 μm and an indentation fracture threshold from 10 to 50 kg.
 11. The glass article of claim 8, wherein the glass article satisfies one or more of: 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1.4; 0.6<[M₂O₃(mol %)/R_(x)O(mol %)]<1; 1.3<[(P₂O₅+R₂O)/M₂O₃]≤2.3; and 1.5<[(P₂O₅+R₂O)/M₂O₃]≤2.0. where M₂O₃=Al₂O₃+B₂O₃, R_(x)O is the sum of monovalent and divalent cation oxides present in the glass composition, and R₂O is the sum of monovalent cation oxides present in the glass composition.
 12. The glass of claim 11, wherein the monovalent and divalent cation oxides are selected from the group consisting of Li₂O, Na₂O, K₂O, Rb₂O, Cs₂O, MgO, CaO, SrO, BaO, and ZnO.
 13. A method of ion exchanging a glass article having a layer under compressive stress, the layer extending from a surface of the glass article to a depth of layer, comprising: providing the glass article of claim 8; and ion exchanging the glass article in a bath at a temperature of up to 410° C. for from 15 minutes to 24 hours to form the layer, wherein the compressive stress of the layer is from 600 MPa to 1200 MPa and the depth of layer is from 10 μm to 40 μm.
 14. A method of making a device comprising a glass article having a layer under compressive stress, the layer extending from a surface of the glass article to a depth of layer, comprising: providing the glass article of claim 8; ion exchanging the glass article in a bath at a temperature of up to 410° C. for from 15 minutes to 24 hours to form the layer, wherein the compressive stress of the layer is from 600 MPa to 1200 MPa and the depth of layer is from 10 μm to 40 μm; and incorporating the glass article into a device. 